磷化电流密度对A286合金电化学磷化膜组织结构和结合强度的影响

A286合金表面易钝化,通过传统化学磷化方法在其表面难以沉积磷化膜,而电化学磷化可避免钝化膜对磷化反应的抑制作用。因此,研究磷化电流密度对磷化膜组织结构和性能的影响规律很有必要。通过电化学磷化首次在A286合金表面形成了致密、高膜基结合力的磷化膜。利用电化学工作站对不同电流密度下磷化过程中电位-时间(ϕ-t)曲线进行测绘,研究电化学磷化膜生长过程的特点;使用扫描电子显微镜(SEM)观察磷化膜的显微组织形貌;使用能谱仪(EDS)分析磷化膜中不同区域的化学成分;使用X射线衍射仪(XRD)研究磷化膜的物相结构;使用划痕仪测定磷化膜与基体的结合力。结果显示:A286合金电化学磷化膜的沉积模式为逐层生长-堆叠的形式。低电流密度下,磷化膜为单一的Hopeite相,组织结构粗大、疏松,膜基结合力约为6 N。随着磷化电流密度的增加,磷化膜逐渐转变为Zn+Hopeite复相,组织结构细化、致密,膜基结合力提高。当阴极电流密度为160 mA/cm^(2)时,膜基结合力高于60 N。综合可知,磷化电流密度的增加有利于电化学磷化膜的致密化,有利于膜基结合力和耐磨性的提高。

表面粗糙度对Q235钢电化学磷化膜耐蚀性的影响

当前的电化学磷化研究忽视了材料表面粗糙度对膜层性能的影响。分别采用机械抛光和高能喷丸对Q235钢进行前处理,并在其表面制备电化学磷化膜;采用扫描电镜、X射线衍射、硫酸铜点滴、全浸泡和极化曲线等方法分析了电化学磷化膜的形貌、组成及耐蚀性。结果表明:粗糙度较小的抛光试样表面形成了块状结晶磷化膜,粗糙度较大的喷丸试样表面形成的电化学磷化膜为细针状结晶;与喷丸处理相比,抛光处理试样表面电化学磷化膜耐蚀性更好,其硫酸铜点滴时间、盐水全浸泡时间和极化电阻分别是喷丸试样的4.0,4.0和3.7倍;喷丸试样膜层主要有Zn3(PO4)2·4H2O、Zn2Fe(PO4)2·4H2O和少量Fe相,而抛光试样中不存在Fe相,出现了耐蚀性更好的Zn3(PO4)2·2H2O相。

电流密度和添加剂对镁合金电化学磷化膜耐蚀性的影响

电化学磷化可以快速获得磷化膜,提高镁合金的耐蚀性,目前就电化学磷化工艺条件对膜层的影响研究尚不深入。为此,采用扫描电镜和电化学方法研究了电流密度和添加剂对镁合金电化学磷化膜耐蚀性的影响。结果显示:电流密度为4.0 A/dm^2时基础磷化液中所得磷化膜表面致密均匀,具有良好的耐蚀性;以0.5 g/L酒石酸和5.0 g/L磷酸二氢钠作为电化学磷化的添加剂可以促进镁合金上磷化膜的生长,单独加入0.5 g/L酒石酸和5.0 g/L磷酸二氢钠时,所得磷化膜颗粒粗糙,将两者按此比例复配加入,所得膜层更加致密,耐蚀性得到提高。

铅-3%锑合金电化学磷化工艺及影响因素研究

提出了一种以锌钙系磷化液为主体的铅-3%锑合金电化学磷化新工艺。电化学测试结果表明:合金经过磷化后,表面形成的磷化膜能有效阻止其在3%NaCl溶液中的腐蚀,使合金的稳定性得到提高。该工艺所用试剂不含有害促进剂,磷化过程无污染,技术环保,具有工业推广价值。

电化学磷化与传统磷化工艺比较

对比了传统磷化与电化学磷化的工艺及磷化膜性能,结果表明电化学磷化能改善磷化膜性能进而极大地提高漆后耐蚀性,且能满足在磷化过程中减少各种沉淀污染物的产生的环保要求。经过工艺改进及完善,电化学磷化工艺可广泛应用于漆前金属表面处理。

碳钢钡系常温电化学磷化工艺

已有的锌锰系电化学磷化工艺药品消耗大,易沉渣,且对环境污染大。采用阴极电化学磷化方法,对碳钢表面进行了钡系常温磷化。通过扫描电镜(SEM)、X射线衍射(XRD)、硫酸铜点滴试验、电化学极化曲线等方法对磷化效果进行了表征。结果表明:采用本工艺可以得到致密的磷化膜,膜的主要成分为磷酸钡和磷酸氢钡;在温度20℃、电流密度0.5 A/dm2下磷化4 min,所得磷化膜耐硫酸铜点滴时间为204 s,耐蚀性良好,优于传统的化学磷化膜。本工艺简单、便于操作,且成膜时间短、速度快,所得膜层耐蚀性优良。

Fe2+对镁合金电化学磷化改性研究

采用FeSO4对电化学磷化膜进行改性,以提高AZ91D镁合金的耐腐蚀性能。通过电化学曲线、X射线衍射仪(XRD)、激光共聚焦显微镜(LSCM)和扫描电子显微镜(SEM)研究了FeSO4添加量对电化学磷化膜表面形貌和耐蚀性的影响。结果表明,磷化液中加入FeSO4后,磷化膜主要组成为Fe4(P2O7)3、Zn3(PO4)2和Mn3(PO4)2。当FeSO4加入量为0.3g/L时,电化学磷化膜腐蚀电位为-1.512V,自腐蚀电流密度为2.346×10^-5A/cm^2,极化电阻为1626.3Ω/cm^2,耐腐蚀性能最好。

不锈钢表面电化学磷化及膜层性能

采用由4.0 g/L ZnO、4 g/L CaCl2、5%(体积分数)H3PO3、4 g/L酒石酸和3 g/L氯酸钠组成的锌钙系磷化液,在温度为70°C和电流密度为4 mA/cm2的条件下对1Cr18Ni9Ti不锈钢表面进行电化学磷化20 min。对比了所得磷化膜与采用相同磷化液化学磷化2 h所得膜层的表面形貌、相结构和耐蚀性。结果表明,与化学磷化相比,电化学磷化所需时间较短,所得膜层的结晶大小和分布均匀,耐腐蚀性更好。

低温快速电化学辅助磷化膜的制备及其耐蚀性

目前国内外关于电化学辅助磷化的研究报道较少。采用硫酸铜点滴试验、塔菲尔极化曲线研究了电化学辅助制备磷化膜的耐蚀性,探究电化学辅助磷化的最佳配方及工艺条件。通过单因素试验优化磷化液组分,通过正交试验优化工艺条件。结果表明,电化学辅助可以显著降低磷化温度、缩短磷化时间、减少磷化渣,优选出的磷化液组成为:5.00 g/L ZnO,13.00 mL/L磷酸(85%),20.00 g/L Zn(NO_3)_2·6H_2O,1.00 g/L酒石酸钾钠,1.00 g/L NH_4HF_2,1.20 g/L NaClO_3,5.00 g/L磷酸二氢锌,0.08 g/L CuSO_4;最优工艺参数为电流密度1.2 A/dm^2,温度35℃,通电时间7 min。最优工艺下所得磷化膜耐硫酸铜点滴试验时间达860 s;磷化时间1 min时,所得磷化膜硫酸铜点滴试验耐蚀性为61 s(远优于化学磷化的19 s),磷化膜外观均匀、致密。

镁合金电化学转化膜的组成及反应机理

目的更好地开展镁合金防腐蚀研究,提高其耐蚀性。方法利用电化学法制备镁合金磷化膜,通过单因素条件实验研究电流密度、温度以及时间对反应过程的影响,得出制备最佳方案。通过X荧光光谱仪(EDX)、X射线衍射仪(XRD)及电化学测试等现代检测技术对镁合金电化学膜微观结构、沉积速率等进行测试,得出制备的转化膜组成成分的定性及半定量分析结果,以此推断镁合金电化学转化膜的生成机理。结果电化学法制备镁合金磷化膜的最佳工艺条件为:电流密度0.5 A/dm2,温度30℃,反应时间5 min。EDX分析结果显示,磷化膜主要成分为Mg、P、Zn,其质量分数分别为11.017%、2.105%、28.534%。结论电化学转化膜的主要化学成分为Mg、P、Zn,还有少量其他成分,如Al、S、Ca、Mn、Ni、Cu。腐蚀机理复杂,不确定性较大。镁合金磷化膜主要由结晶型磷化锌、磷化铝、锌镁金属磷化夹杂物和单质Zn组成,并且还有少量的其他化合物。

Corrosion resistance of cerium-doped zinc calcium phosphate chemical conversion coatings on AZ31 magnesium alloy

Zinc calcium phosphate （Zn-Ca-P） coating and cerium-doped zinc calcium phosphate （Zn-Ca-Ce-P） coating were prepared on AZ31 magnesium alloy. The chemical compositions, morphologies and corrosion resistance of coatings were investigated through energy-dispersive X-ray spectroscopy （EDS）, X-ray photoelectron spectroscopy （XPS）, X-ray diffraction （XRD）, electron probe micro-analysis （EPMA） and scanning electron microscopy （SEM） together with hydrogen volumetric and electrochemical tests. The results indicate that both coatings predominately contain crystalline hopeite （Zn3（PO4）2·4H2O）, Mg3（PO4）2 and Ca3（PO4）2, and traces of non-crystalline MgF2 and CaF2. The Zn-Ca-Ce-P coating is more compact than the Zn-Ca-P coating due to the formation of CePO4, and displays better corrosion resistance than the Zn-Ca-P coating. Both coatings protect the AZ31 Mg substrate only during an initial immersion period. The micro-galvanic corrosion between the coatings and their substrates leads to an increase of hydrogen evolution rate （HER） with extending the immersion time. The addition of Ce promotes the homogenous distribution of Ca and formation of hopeite. The Zn-Ca-Ce-P coating has the potential for the primer coating on magnesium alloys.

Progress of electroplating and electroless plating on magnesium alloy

The current research processes of electroplating and electroless Ni-P alloy plating on magnesium alloys were reviewed. Theoretically,the reason for difficulties in electroplating and electroless plating on magnesium alloys was given.The zinc immersion, copper immersion,direct electroless Ni-P alloy plating and electroplating and electroless plating on magnesium alloys prepared by chemical conversion coating were presented in detail.Especially,the research development of magnesium alloy AZ91 and AZ31 was discussed briefly.Based on the analysis,the existing problems and future research directions were then given.

Degradation of Soil Properties due to Erosion on Sloping Land in Southern Jiangsu Province,China

Soil erosion accelerates soil degradation. Some natural soils and cultivated soils on sloping land in southern Jiangsu Province, China were chosen to study soil degradation associated with erosion. Soil erosion intensity was investigated using the 137Cs tracer method. Soil particle-size distribution, soil organic matter (OM), total nitrogen (TN) and total phosphorus (TP) were measured, and the effects of erosion on soil physical and chemical properties were analyzed statistically using SYSTAT8.0. Results indicated that erosion intensity of cultivated soils was greater than that of the natural soils, suggesting that cultivation increased soil loss. Erosion also led to an increase of coarser soil particle proportion, especially in natural soils. In addition, silt was the primary soil particle lost due to erosion. However, in cultivated fields, coarser soil particles over time were attributed not only to soil erosion but also to mechanical eluviation as a result of farming activities. Moreover, erosion caused a decrease in soil OM, TN and TP as well as thinning of the soil layer.

Spatial and Temporal Variability of N, P and K Balances for Agroecosystems in China

Nitrogen, phosphorus, and potassium balances for agroecosystems in China from 1993 to 2001 were calculated at national and provincial levels using statistical data and related parameters, and their spatial and temporal variabilities were analyzed with GIS to estimate the potential impacts of nutrient N, P and K surpluses or deficits to soil, water and air. At the national scale, the N and P balances from 1993 to 2001 showed a surplus, with the nitrogen surplus remaining relatively stable from 1997—2001. Although during this period the P surplus pattern was similar to N, it had smaller values and kept increasing as the use of phosphate fertilizer increased year by year. However, K was deficient from 1993 to 2001 even though from 1999 to 2001 the K deficit decreased. The spatial analysis revealed higher N surpluses in the more developed southeastern provinces and lowest in the western and northern provinces where there was less chemical fertilizer input. The serious K deficit mainly occurred in Shanghai and Beijing municipalities, Jiangsu, Zhejiang and Hubei provinces, and Xinjiang autonomous regions. For the years 1992, 1996 and 2001, N surpluses and K deficits had significant positive spatial correlations with per capita gross domestic product (GDP), per capita gross industrial output value, and per capita net income of rural households. This showed that the level of economic development played an important role on nutrient balances in the agroecosystems.

Effects of Sr incorporation on surface structure and corrosion resistance of hydroxyapatite coated Mg-4Zn alloy for biomedical applications

Hydroxyapatite（HA） and strontium（Sr） incorporated HA coatings with different Sr contents were prepared on Mg-4 Zn substrates by electrochemical deposition method. Fourier transform infrared（FTIR） spectroscopy, X-ray diffraction（XRD）, scanning electron microscopy（SEM）, energy dispersive spectroscopy（EDS） and electrochemical workstation were applied for the composition, phase constitution, morphology analyses and corrosion tests. The results reveal that the incorporation of Sr in coatings does not lead to dramatical change of functional groups and the crystal structure of the HA phase, but the crystal size and crystallinity decrease with increasing Sr content, which should be attributed to the lattice distortion and different occupancies of Sr and Ca ions. The 10 Sr HA@Mg-4 Zn samples show the lowest corrosion current density and the highest corrosion potential, and also exhibit the lowest amount of hydrogen evolution among all coated samples.

高水分玉米安全度夏储粮试验

在房式仓内储存14.8%的高水分玉米,通过采用聚乙烯塑料膜密闭,结合磷化铝化学熏蒸使粮堆内保持有效磷化氢浓度,抑制了霉、虫孳生,确保了高水分玉米安全度夏。

Effects of Hg and Cu on the activities of soil acid phosphatase

Comparative study on the activity and kinectic properties of acid phosphatase （ACPase） of three soils amended with Hg and Cu at constant temperature and humidity was carried out. The results indicated that the inhibition on ACPase of the three sample soils by Hg and Cu varied with the content of soil organic matter and pH, where, Soil 1 was the most seriously contaminated due to its lowest content of organic matter and the lowest pH among three samples, Soil 2 took the second place, and Soil 3 was the least contaminated. Except Soil 3, the activity of soil ACPase tended to increase along with the contact time under the same type and the same concentration of heavy metal. In particular the Vmax values of ACPase in all three samples decreased with increasing Hg and Cu concentration, whereas the Km values were affected weakly. According to the change of Vmax and Km values, Cu and Hg had the same inhibition effect on soil ACPase. Both of them may he a type of compound of non-competitive and anti-competitive inhibition. Statistic analyses indicated that activities of soil ACPase and Vmax values could serve as bioindicator to partially denote the heavy metal Hg and Cu contamination degree.

A Study on Stoichiometry of Complexes of Tributyl Phosphate and Methyl Isobutyl Ketone with Lithium in the Presence of FeCl_3

To study the characteristic of liquid-liquid extraction equilibrium of lithium from brine sources, the complexes formed from tributyl phosphate （TBP） and methyl isobutyl ketone （MIBK） with lithium were investi- gated using FeCl3 as coextracting agent. Liquid-liquid extraction reaction mechanisms were proposed and the stoichiometry of tetrachloroferrate（III） complex with lithium was obtained by regressing the experimental data. It is found that the stoichiometry of tetrachloroferrate（III） to lithium in the complex is 1 ： 1 with either TBP or MIBK as extractant in kerosene. The stoichiometry of the complex of TBP with Li was 1 ： 1 and that of MIBK with Li was 2 ： 1. The formed complexes of TBP and MIBK with lithium are determined to be LiFeCla-TBP and LiFeC14.2MIBK, respectively, according to the rule of neutralization.

The Search for New Methods of Synthesis Possible of Organometallic Compounds of P, As, Sb, Bi

The authors spent the search for new methods of synthesis possible of organometallic compounds of phosphorus, arsenic, antimony, bismuth. For modifications classical reactions the N （nitrogen） atoms have been replaced on atoms of P （phosphorus）, As （arsenic）, Sb （antimony） and Bi （bismuth）. The authors have proposed a new mechanism for the possible reactions.